Fuel additives derived from amido-amines

ABSTRACT

The present invention is directed to a fuel additive comprising at least one adduct of (A) a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 (e.g., from about 1 to 4) mono- or dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule, (B) an amido-amine or thioamido-amine characterized by being a reaction product of at least a polyamine and an alpha, beta-unsaturated compound of the formula: ##STR1## wherein X is sulfur or oxygen, Y is --OR 4 , --SR 4 , or --NR 4  (R 5 ) , and R 1 , R 2 , R 3 , R 4  and R 5  are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.

This is a continuation of application Ser. No. 358,731, filed May 30,1989 now U.S. Pat. No. 5,034,018, which is a continuation-in-part ofSer. No. 07/126,405, filed Nov. 30, 1987, now U.S. Pat. No. 4,857,217,which is a continuation-in-part of Ser. No. 07/178,099 filed Apr. 6,1988, now U.S. Pat. No. 4,963,275, which is a continuation-in-part of07/269,461, filed Nov. 10, 1988, now U.S. Pat. No. 4,956,107, which is acontinuation-in-part of Ser. No. 06/916,218, filed Oct. 7, 1986 nowabandoned.

FIELD OF THE INVENTION

This invention relates to improved oil soluble dispersant additivesuseful in fuel compositions, and to concentrates containing saidadditives.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 2,921,085 relates to the preparation ofbeta-aminopropionamides by reaction of an alkyl amine with an acrylateto form an alkyl aminopropionate and reaction of the latter compoundwith an amine. The resulting compounds are disclosed to have utility assurface active agents, specifically as emulsifying, wetting, foaming anddetergent agents

U.S. Pat. No. 3,337,609 relates to adducts of hydroxyalkyl alkylenepolyamines and acrylates. The resulting adducts are added topolyepoxides to provide compositions which are suitable for use as abarrier coating for polyethylene surfaces, and for additional end uses,such as in molding. In addition, the adducts are disclosed to be usefulas catalysts in resin preparation and as corrosion inhibitors in watersystems for ferrous metals.

U.S. Pat. No. 3,417,140 relates to the preparation of amido-aminecompositions, which are useful as epoxy resin curing agents, by reactinga polyalkylene polyamine and a fatty amine (comprising a mono- ordiamine having as one of the substituents on a nitrogen atom ahydrocarbyl radical having 8 to 24 carbon atoms) with an alpha-betaunsaturated carbonylic compound. It is disclosed that this reactionoccurs through the Michael addition of an amine group across theunsaturated group of the carbonylic compound and through thecondensation of an amine group with the carbonylic group.

U.S. Pat. No. 3,247,163 also relates to curing agents for polyepoxidecompositions, which curing agents are prepared by reacting an organicamine and an acrylate.

U.S. Pat. No. 3,445,441 relates to amino-amido polymers characterized bybeing a reaction product of at least a polyamine and an acrylate typecompound, such as methyl or ethyl acrylate, and methyl or ethylmethacrylate. The patent states that the polymers are useful in a widevariety of applications, such as floculating agents, water clarifyingadditives, corrosion inhibitors in oil and gas wells, and as lube oiladditives. The patent further discloses that the polymers may bederivitized, including acylation with monocarboxylic acids andpolycarboxylic acids, aliphatic dicarboxylic acids, aromaticdicarboxylic acids, for example, diglycolic, phthalic, succinic, etc.,acids.

U.S. Pat. No. 3,903,003 relates to lubricating compositions containingan amido-amine reaction product of a terminally carboxylated isoprenepolymer which is formed by reacting a terminally carboxylatedsubstantially completely hydrogenated polyisoprene having an averagemolecular weight between about 20,000 and 250,000 and a nitrogencompound of the group consisting of polyalkylene amines and hydroxylpolyalkylene amines.

U.S. Pat. No. 4,493,771 relates to scale inhibiting with compoundscontaining quaternary ammonium and methylene phosphonic acid groups.These compounds are derivatives of polyamines in which the aminehydrogens have been substituted with both methylene phosphonic acidgroups or their salts and hydroxypropyl quaternary ammonium halidegroups. The patent discloses that any amine that contains reactive aminohydrogens can be utilized, for example, polyglycol amines, amido-amines,oxyacylated amines, and others.

U.S. Pat. No. 4,459,241 contains a similar disclosure to U.S. Pat. No.4,493,771.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to a dispersantfuel additive comprising at least one adduct of (A) an amido-aminecharacterized by being a reaction product of at least a polyamine and analpha, beta unsaturated compound of the formula: ##STR2## wherein X issulfur or oxygen, Y is --OR⁴, --SR⁴, or --NR⁴ (R⁵) , and R¹, R², R³, R⁴and R⁵ are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl, and (B) a polyolefin of 300 to 10,000 numberaverage molecular weight substituted with at least 0.3 (e.g., from about1 to 4) mono- or dicarboxylic acid producing moieties (preferably acidor anhydride moieties) per polyolefin molecule.

The materials of the invention are different from the prior art becauseof their effectiveness and their ability to provide enhanceddispersancy. In crankcase lubricating oils, these additives have proventheir ability to provide surprising enhanced performance as judged bythe commercial 5E gasoline engine performance test. In fuels, theadditives serve to minimize the degree of carburetor and fuel injectorfouling from deposits.

Therefore, the present invention is also directed to novel processes forpreparing the dispersant fuel adducts of this invention.

DETAILED DESCRIPTION OF THE INVENTION PREPARATION OF AMIDO-AMINEREACTANT A

As described above, the amido-amine comprises a reaction product of atleast a polyamine and an alpha, beta ethylenically unsaturated compoundof formula (I) above.

The polyamines useful in this invention comprise polyamines, mostpreferably polyalkylene polyamines, of about 2 to 60, preferably 2 to 40(e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to12, and most preferably at least 5 (e.g., 5 to 9) nitrogen atoms in themolecule. These amines may be hydrocarbyl amines or may be hydrocarbylamines including other groups, e.g, hydroxy groups, alkoxy groups, amidegroups, nitriles, imidazoline groups, and the like. Hydroxy amines with1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularlyuseful. Preferred amines are aliphatic saturated amines, including thoseof the general formulas: ##STR3## wherein R, R', R'' and R''' areindependently selected from the group consisting of hydrogen; C₁ to C₂₅straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy C₂ to C₆alkylene radicals; C₂ to C₁₂ hydroxy amino alkylene radicals; and C₁ toC₁₂ alkylamino C₂ to C₆ alkylene radicals; and wherein R"' canadditionally comprise a moiety of the formula: ##STR4## wherein R' is asdefined above, and wherein s and s' can be the same or a differentnumber of from 2 to 6, preferably 2 the same or a different number offrom 2 to 6, preferably 2 to 4; and t and t' can be the same ordifferent and are numbers of from 0 to 10, preferably 2 to 7, and mostpreferably about 3 to 7, with the proviso that the sum of t and t' isnot greater than 15. To assure a facile reaction, it is preferred thatR, R', R'', R''', s, s', t and t' be selected in a manner sufficient toprovide the compounds of Formulas II and III with typically at least oneprimary or secondary amine group, preferably at least two primary orsecondary amine groups. This can be achieved by selecting at least oneof said R, R', R" or R''' groups to be hydrogen or by letting t inFormula III be at least one when R"' is H or when the IV moietypossesses a secondary amino group. The most preferred amine of the aboveformulas are represented by Formula III and contain at least two primaryamine groups and at least one, and preferably at least three, secondaryamine groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene)triamine;di-(1,3-propylene) triamine; N ,N-dimethyl-1,3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine;N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, andtri-tallow amines; amino morpholines such asN-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula (V): ##STR5## wherein p₁ and p₂ are the same or different andare each integers of from 1 to 4, and n₁, n₂ and n₃ are the same ordifferent and are each integers of from 1 to 3. Non-limiting examples ofsuch amines include 2-pentadecyl imidazoline: N-(2-aminoethyl)piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an involves the reaction of an alkylene dihalide (such as ethylenedichloride or propylene dichloride) with ammonia, which results in acomplex mixture of alkylene amines wherein pairs of nitrogens are joinedby alkylene groups, forming such compounds as diethylene triamine,triethylenetetramine, tetraethylene pentamine and isomeric piperazines.Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogenatoms per molecule are available commercially under trade names such as"Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formulae: ##STR6## where m has a value of about 3 to 70 andpreferably 10 to 35; and ##STR7## where "n" has a value of about 1 to 40with the provision that the sum of all the n's is from about 3 to about70 and preferably from about 6 to about 35, and R is a polyvalentsaturated hydrocarbon radical of up to ten carbon atoms wherein thenumber of substituents on the R group is represented by the value of"a", which is a number of from 3 to 6. The alkylene groups in eitherformula (VI) or (VII) may be straight or branched chains containingabout 2 to 7, and preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamines of formulas (VI) or (VII) above,preferably polyoxyalkylene diamines and polyoxyalkylene triamines, mayhave average molecular weights ranging from about 200 to about 4000 andpreferably from about 400 to about 2000. The preferred polyoxyalkylenepolyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.

Additional amines useful in the present invention are described in U.S.Pat. No. 3,445,441, the disclosure of which is hereby incorporated byreference in its entirety.

Thus, any polyamine , whether aliphatic, cycloaliphatic, aromatic,heterocyclic, etc., can be employed provided it is capable of addingacross the acrylic double bond and amidifying with for example thecarbonyl group (--C(O)--) of the acrylate-type compound of formula I, orwith the thiocarbonyl group (--C(S)--) of the thioacrylate-type compoundof formula I.

The alpha, beta ethylenically unsaturated compounds employed in thisinvention comprise at least one member selected from the groupconsisting of alpha, beta ethylenically unsaturated compounds of theformula ##STR8## wherein X is sulfur or oxygen, Y is --OR⁴, --SR⁴, or--NR⁴ (R⁵) , and R¹, R², R³, R⁴ and R⁵ are the same or different and arehydrogen or substituted or unsubstituted hydrocarbyl.

When R¹, R², R³, R⁴ or R⁵ are hydrocarbyl, these groups can comprisealkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic, which can besubstituted with groups which are substantially inert to any componentof the reaction mixture under conditions selected for preparation of theamido-amine. Such substituent groups include hydroxy, halide (e.g., Cl,Fl, I, Br), --SH and alkylthio. When one or more of R¹ through R⁵ arealkyl, such alkyl groups can be straight or branched chain, and willgenerally contain from 1 to 20, more usually from 1 to 10, andpreferably from 1 to 4, carbon atoms. Illustrative of such alkyl groupsare methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one ormore of R¹ through R⁵ are aryl, the aryl group will generally containfrom 6 to 10 carbon atoms (e.g., phenyl, naphthyl).

When one or more of R¹ through R⁵ are alkaryl, the alkaryl group willgenerally contain from about 7 to 20 carbon atoms, and preferably from 7to 12 carbon atoms. Illustrative of such alkaryl groups are tolyl,m-ethylphenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R¹through R⁵ are aralkyl, the aryl component generally consists of phenylor (C₁ to C₆) alkyl-substituted phenol and the alkyl component generallycontains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbonatoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and4-isobutylbenzyl. When one or more of R¹ and R⁵ are cycloalkyl, thecycloalkyl group will generally contain from 3 to 12 carbon atoms, andpreferably from 3 to 6 carbon atoms. Illustrative of such cycloalkylgroups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, andcyclododecyl. When one or more of R¹ through R⁵ are heterocyclic, theheterocyclic group generally consists of a compound having at least onering of 6 to 12 members in which on one more ring carbon atoms isreplaced by oxygen or nitrogen. Examples of such heterocyclic groups arefuryl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyland 1,4-oxazinyl.

The alpha, beta ethylenically unsaturated carboxylate compounds employedherein have the following formula: ##STR9## wherein R¹, R², R³, and R⁴are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl as defined above. Examples of such alpha,beta-ethylenically unsaturated carboxylate compounds of formula VIII areacrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl,and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid,2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid,3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid,3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid,2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid,2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid,2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate,methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate,dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl3-phenyl-2-propenoate, and the like.

The alpha, beta ethylenically unsaturated carboxylate thioestercompounds employed herein have the following formula: ##STR10## whereinR¹, R², R³, and R⁴ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofsuch alpha, beta-ethylenically unsaturated carboxylate thioesters offormula IX are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate,isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiarybutylmercapto 2-propenoate, octadecylmercapto 2-propenoate,dodecylmercapto 2-decenoate, cyclopropylmercapto2,3-dimethyl-2-butenoate, methylmercapto 3-phenyl-2-propenoate,methylmercapto 2-propenoate, methylmercapto 2-methyl-2-propenoate, andthe like.

The alpha, beta ethylenically unsaturated carboxyamide compoundsemployed herein have the following formula: ##STR11## wherein R¹, R²,R³, R⁴ and R⁵ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated carboxyamides of formula X are2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide,3-methyl-2-butenamide, 3-phenyl-2-propenamide,3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide,2-propyl-2-propenamide, 2-isopropyl-2-hexenamide,2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl 2-decenamide,N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide, N-octadecyl2-propenamide, N-N-didodecyl 2-decenamide, N-cyclopropyl2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide,2-propenamide, 2-methyl-2-propenamide, 2-ethyl-2-propenamide and thelike.

The alpha, beta ethylenically unsaturated thiocarboxylate compoundsemployed herein have the following formula: ##STR12## wherein R¹, R²,R³, and R⁴ are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated thiocarboxylate compounds of formula XIare 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid,3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid,3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid,2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid,2-isopropyl-2-hexenthioic acid, 2,3-dimethyl-2-butenthioic acid,3-cyclohexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenthioate,ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate,tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl3-phenyl-2-propenthioate, and the like.

The alpha, beta ethylenically unsaturated dithioic acid and acid estercompounds employed herein have the following formula: ##STR13## whereinR¹, R², R³, and R⁴ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofalpha, beta-ethylenically unsaturated dithioic acids and acid esters offormula XII are 2-butendithioic acid, 2-hexendithioic acid,2-decendithioic acid, 3-methyl-2-heptendithioic acid,3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid,3-cyclohexyl-2-butendithioic acid, 2 -methyl-2 -butendithioic acid,2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid,2,3-dimethyl-2-butendithioic acid,3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid,methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate,phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl2-propendithioate, dodecyl 2-decendithioate, cyclopropyl2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, andthe like.

The alpha, beta ethylenically unsaturated thiocarboxyamide compoundsemployed herein have the following formula: ##STR14## wherein R¹, R²,R³, and R⁴ and R⁵ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofalpha, beta-ethylenically unsaturated thiocarboxyamides of formula XIIIare 2-butenthioamide, 2-hexenthioamide, 2-decenthioamide,3-methyl-2-heptenthioamide, 3-methyl-2-heptenthioamide,3-methyl-2-butenthioamide, 3-phenyl-2-propenthioamide,3-cyclohexyl-2-butenthioamide, 2-methyl-2-butenthioamide,2-propyl-2-propenthioamide, 2-isopropyl-2-hexenthioamide,2,3-dimethyl-2-butenthioamide, 3-cyclohexyl-2-methyl-2-pententhioamide,N-methyl 2-butenthioamide, N,N-diethyl 2-hexenthioamide, N-isopropyl2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl2-propenthioamide, N-octadecyl 2-propenthioamide, N-N-didodecyl2-decenthioamide, N-cyclopropyl 2,3-dimethyl-2-butenthioamide, N-methyl3-phenyl-2-propenthioamide, 2-propenthioamide,2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamide and the like.

Preferred compounds for reaction with the polyamines in accordance withthis invention are lower alkyl esters of acrylic and (lower alkyl)substituted acrylic acid. Illustrative of such preferred compounds arecompounds of the formula: ##STR15## where R³ is hydrogen or a C₁ to C₄alkyl group, such as methyl, and R⁴ is hydrogen or a C₁ to C₄ alkylgroup, capable of being removed so as to form an amido group, forexample, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,aryl, hexyl, etc. e.g., propyl acrylate and propyl methacrylate In thepreferred embodiments these compounds are acrylic and methacrylic esterssuch as methyl or ethyl acrylate, methyl or ethyl methacrylate When theselected alpha, beta-unsaturated compound comprises a compound offormula I wherein X is oxygen, the resulting reaction product with thepolyamine contains at least one amido linkage (--C(O)N<) and suchmaterials are herein termed "amido-amines." Similarly, when the selectedalpha, beta unsaturated compound of formula I comprises a compoundwherein X is sulfur, the resulting reaction product with the polyaminecontains thioamide linkage (--C(S)N<) and these materials are hereintermed "thioamido-amines." For convenience, the following discussion isdirected to the preparation and use of amido-amines, although it will beunderstood that such discussion is also applicable to thethioamido-amines.

The type of amido-amine formed varies with reaction conditions. Forexample, a more linear amido-amine is formed where substantiallyequimolar amounts of the unsaturated carboxylate and polyamine arereacted. The presence of excesses of the ethylenically unsaturatedreactant of formula I tends to yield an amido-amine which is morecross-linked than that obtained where substantially equimolar amounts ofreactants are employed. Where for economic or other reasons across-linked amido-amine using excess amine is desired, generally amolar excess of the ethylenically unsaturated reactant of about at least10%, such as 10-300%, or greater, for example, 25-200%, is employed. Formore efficient cross-linking an excess of carboxylated material shouldpreferably be used since a cleaner reaction ensues. For example, a molarexcess of about 10-100% or greater such as 10-50%, but preferably anexcess of 30-50%, of the carboxylated material. Larger excess can beemployed if desired.

In summary, without considering other factors, equimolar amounts ofreactants tend to produce a more linear amido-amine whereas excess ofthe formula I reactant tends to yield a more cross-linked amido-amine.It should be noted that the higher the polyamine (i.e., in greater thenumber of amino groups on the molecule) the greater the statisticalprobability of cross-linking since, for example, atetraalkylenepentamine, such as tetraethylene pentamine ##STR16## hasmore labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido andamino groups. In their simplest embodiments they may be represented byunits of the following idealized formula: ##STR17## wherein the R's,which may be the same or different, are hydrogen or a substituted group,such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl,etc., and A is a moiety of the polyamine which, for example, may bearyl, cycloalkyl, alkyl, etc., and n is an integer such as 1-10 orgreater. The amido-amine adducts preferably contain an average of from 1to 3 amido groups per molecule of the amido-amine adduct.

The above simplified formula represents a linear amido-amine polymer.However, cross-linked polymers may also be formed by employing certainconditions since the polymer has labile hydrogens which can furtherreact with either the unsaturated moiety by adding across the doublebond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines of this invention are notcross-linked to any substantial degree, and more preferably aresubstantially linear.

Preferably, the polyamine reactant contains at least one primary amine(and more preferably from 2 to 4 primary amines) group per molecule, andthe polyamine and the unsaturated reactant of formula I are contacted inan amount of from about 1 to 10, more preferably from about 2 to 6, andmost preferably from about 3 to 5, equivalents of primary amine in thepolyamine reactant per mole of the unsaturated reactant of formula I.

The reaction between the selected polyamine and acrylate-type compoundis carried out at any suitable temperature. Temperatures up to thedecomposition points of reactants and products can be employed. Inpractice, one generally carries out the reaction by heating thereactants below 100° C., such as 80°-90° C., for a suitable period oftime, such as a few hours Where an acrylic-type ester is employed, theprogress of the reaction can be judged by the removal of the alcohol informing the amide. During the early part of the reaction alcohol isremoved quite readily below 100° C. in the case of low boiling alcoholssuch as methanol or ethanol. As the reaction slows, the temperature israised to push the polymerization to completion and the temperature maybe raised to 150° C. toward the end of the reaction. Removal of alcoholis a convenient method of judging the progress and completion of thereaction which is generally continued until no more alcohol is evolved.Based on removal of alcohol, the yields are generally stoichiometric. Inmore difficult reactions, yield of at least 95% are generally obtained.

Similarly, it will be understood that the reaction of an ethylenicallyunsaturated carboxylate thioester of formula IX liberates thecorresponding HSR⁴ compound (e.g., H₂ S when R⁴ is hydrogen) as aby-product, and the reaction of an ethylenically unsaturatedcarboxyamide of formula X liberates the corresponding HNR⁴ (R⁵) compound(e.g., ammonia when R⁴ and R⁵ are each hydrogen) as by-product.

The reaction time involved can vary widely depending on a wide varietyof factors. For example, there is a relationship between time andtemperature. In general, lower temperature demands longer times.Usually, reaction times of from about 2 to 30 hours, such as 5 to 25hours, and preferably 3 to 10 hours will be employed.

Although one can employ a solvent, the reaction can be run without theuse of any solvent. In fact, where a high degree of cross-linking isdesired, it is preferably to avoid the use of a solvent and mostparticularly to avoid a polar solvent such as water. However, takinginto consideration the effect of solvent on the reaction, where desired,any suitable solvent can be employed, whether organic or inorganic,polar or non-polar.

As an example of the amido-amine adducts, the reaction of tetraethylenepentaamine (TEPA) with methyl methacrylate can be illustrated asfollows: ##STR18##

PREPARATION OF REACTANT B

As indicated above, the fuel dispersant materials of this invention canbe prepared by reacting the amidoamine A with a hydrocarbyl-substitutedacid, anhydride or ester material. The long chain hydrocarbylpolymer-substituted mono- or dicarboxylic acid material, i.e., acid,anhydride or acid ester used in this invention, includes the reactionproduct of a long chain hydrocarbon polymer, generally a polyolefin,with a monounsaturated carboxylic reactant comprising at least onemember selected from the group consisting of (i) monounsaturated C₄ toC₁₀ dicarboxylic acid (preferably wherein (a) the carboxyl groups arevicinyl, (i.e. located on adjacent carbon atoms) and (b) at least one,preferably both, of said adjacent carbon atoms are part of said monounsaturation); (ii) derivatives of (i) such as anhydrides or C₁ to C₅alcohol derived mono- or di-esters of (i); (iii) monounsaturated C₃ toC₁₀ monocarboxylic acid wherein the carbon-carbon double bond isconjugated to the carboxy group, i.e, of the structure ##STR19## and(iv) derivatives of (iii) such as C₁ to C₅ alcohol derived monoesters of(iii). Upon reaction with the polymer, the monounsaturation of themonounsaturated carboxylic reactant becomes saturated. Thus, forexample, maleic anhydride becomes a polymer substituted succinicanhydride, and acrylic acid becomes a polymer substituted propionicacid.

Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferablyfrom about 1.0 to about 2.0, and most preferably from about 1.1 to about1.7 moles of said monounsaturated carboxylic reactant are charged to thereactor per mole of polymer charged

Normally, not all of the polymer reacts with the monounsaturatedcarboxylic reactant and the reaction mixture will contain non-acidsubstituted polymer. The polymer-substituted mono- or dicarboxylic acidmaterial (also referred to herein as "functionalized" polymer orpolyolefin), non-acid substituted polyolefin, and any other polymericby-products, e.g. chlorinated polyolefin, (also referred to herein as"unfunctionalized" polymer) are collectively referred to herein as"product residue" or "product mixture". The non-acid substituted polymeris typically not removed from the reaction mixture (because such removalis difficult and would be commercially infeasible) and the productmixture, stripped of any monounsaturated carboxylic reactant is employedfor further reaction with the amine or alcohol as described hereinafterto make the dispersant.

Characterization of the average number of moles of monounsaturatedcarboxylic reactant which have reacted per mole of polymer charged tothe reaction (whether it has undergone reaction or not) is defined herein as functionality. Said functionality is based upon (i) determinationof the saponification number of the resulting product mixture usingpotassium hydroxide; and (ii) the number average molecular weight of thepolymer charged, using techniques well known in the art. Functionalityis defined solely with reference to the resulting product mixture.Although the amount of said reacted polymer contained in the resultingproduct mixture can be subsequently modified, i.e. increased ordecreased by techniques known in the art, such modifications do notalter functionality as defined above. The terms "polymer substitutedmonocarboxylic acid material" and "polymer substituted dicarboxylic acidmaterial" as used herein are intended to refer to the product mixturewhether it has undergone such modification or not.

Accordingly, the functionality of the polymer substituted mono- anddicarboxylic acid material will be typically at least about 0.3,preferably at least about 0.8, and most preferably at least about 0.9and will vary typically from about 0.5 to about 2.8 (e.g., 0.6 to 2),preferably from about 0.8 to about 1.4, and most preferably from about0.9 to about 1.3.

Exemplary of such monounsaturated carboxylic reactants are fumaric acid,itaconic acid, maleic acid, maleic anhydride, chloromaleic acid,chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid,cinnamic acid, and lower alkyl (e.g., C₁ to C₄ alkyl) acid esters of theforegoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.

Preferred olefin polymers for reaction with the monounsaturatedcarboxylic reactants to form reactant A are polymers comprising a majormolar amount of C₂ to C₁₀, e.g. C₂ to C₅ monoolefin. Such olefinsinclude ethylene, propylene, butylene, isobutylene, pentene, octene-1,styrene, etc. The polymers can be homopolymers such as polyisobutylene,as well as copolymers of two or more of such olefins such as copolymersof: ethylene and propylene; butylene and isobutylene; propylene andisobutylene; etc. Mixtures of polymers prepared by polymerization ofmixtures of isobutylene, butene-1 and butene-2, e.g., polyisobutylenewherein up to about 40% of the monomer units are derived from butene-1and butene-2, is an exemplary, and preferred, olefin polymer Othercopolymers include those in which a minor molar amount of the copolymermonomers, e.g., 1 to 10 mole %, is a C₄ to C₁₈ non-conjugated diolefin,e.g., a copolymer of isobutylene and butadiene; or a copolymer ofethylene, propylene and 1,4-hexadiene; etc.

In some cases, the olefin polymer may be completely saturated, forexample an ethylene-propylene copolymer made by a Ziegler-Nattasynthesis using hydrogen as a moderator to control molecular weight

The olefin polymers used in the formation of reactant B will have numberaverage molecular weights within the range of about 300 to 10,000,generally from about 700 and about 5,000, preferably from about 1000 to4,000, more preferably between about 1300 and about 3,000. Particularlyuseful olefin polymers have number average molecular weights within therange of about 1500 and about 3000 with approximately one terminaldouble bond per polymer chain. An especially useful starting materialfor highly potent dispersant additives useful in accordance with thisinvention is polyisobutylene, wherein up to about 40% of the monomerunits are derived from butene-1 and/or butene-2. The number averagemolecular weight for such polymers can be determined by several knowntechniques. A convenient method for such determination is by gelpermeation chromatography (GPC) which additionally provides molecularweight distribution information, see W. W. Yau, J. J. Kirkland and D. D.Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons,New York, 1979.

The olefin polymers will generally have a molecular weight distribution(the ratio of the weight average molecular weight to number averagemolecular weight, i.e. M_(w) /M_(n)) of from about 1.0 to 4.5, and moretypically from about 1.5 to 3.0.

The polymer can be reacted with the monounsaturated carboxylic reactantby a variety of methods. For example, the polymer can be firsthalogenated, chlorinated or brominated to about 1 to 8 wt. %, preferably3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, bypassing the chlorine or bromine through the polymer at a temperature of60° to 250° C., preferably 110° to 160° C., e.g. 120° to 140° C., forabout 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer maythen be reacted with sufficient monounsaturated carboxylic reactant at100° to 250° C., usually about 180° to 235° C., for about 0.5 to 10,e.g. 3 to 8 hours, so the product obtained will contain the desirednumber of moles of the monounsaturated carboxylic reactant per mole ofthe halogenated polymer. Processes of this general type are taught inU.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.Alternatively, the polymer and the monounsaturated carboxylic reactantare mixed and heated while adding chlorine to the hot material.Processes of this type are disclosed in U.S. Pat. Nos. 3,215,707;3,231,587; 3,912,764; 4,110,349; 4,234,435; and in U.K. 1,440,219.

Alternately, the polymer and the monounsaturated carboxylic reactant canbe contacted at elevated temperature to cause a thermal "ene" reactionto take place. Thermal "ene" reactions have been heretofore described inU.S. Pat. Nos. 3,361,673 and 3,401,118, the disclosures of which arehereby incorporated by reference in their entirety.

Preferably, the polymers used in this invention contain less than 5 wt%, more preferably less than 2 wt %, and most preferably less than 1 wt% of a polymer fraction comprising polymer molecules having a molecularweight of less than about 300, as determined by high temperature gelpremeation chromatography employing the corresponding polymercalibration curve. Such preferred polymers have been found to permit thepreparation of reaction products, particularly when employing maleicanhydride as the unsaturated acid reactant, with decreased sediment Inthe event the polymer produced as described above contains greater thanabout 5 wt % of such a low molecular weight polymer fraction, thepolymer can be first treated by conventional means to remove the lowmolecular weight fraction to the desired level prior to initiating theene reaction, and preferably prior to contacting the polymer with theselected unsaturated carboxylic reactant(s). For example, the polymercan be heated, preferably with inert gas (e.g., nitrogen) stripping, atelevated temperature under a reduced pressure to volatilize the lowmolecular weight polymer components which can then be removed from theheat treatment vessel. The precise temperature, pressure and time forsuch heat treatment can vary widely depending on such factors as thepolymer number average molecular weight, the amount of the low molecularweight fraction to be removed, the particular monomers employed andother factors. Generally, a temperature of from about 60° to 100° C. anda pressure of from about 0.1 to 0.9 atmospheres and a time of from about0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.

In this process, the selected polymer and monounsaturated carboxylicreactant and halogen (e.g., chlorine gas), where employed, are contactedfor a time and under conditions effective to form the desired polymersubstituted mono- or dicarboxylic acid material. Generally, the polymerand monounsaturated carboxylic reactant will be contacted in aunsaturated carboxylic reactant to polymer mole ratio usually from about0.7:1 to 4:1, and preferably from about 1:1 to 2:1, at an elevatedtemperature, generally from about 120° to 260° C., preferably from about160° to 240° C. The mole ratio of halogen to monounsaturated carboxylicreactant charged will also vary and will generally range from about0.5:1 to 4:1, and more typically from about 0.7:1 to 2:1 (e.g., fromabout 0.9 to 1.4:1). The reaction will be generally carried out, withstirring for a time of from about 1 to 20 hours, preferably from about 2to 6 hours.

By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g.polyisobutylene will normally react with the monounsaturated carboxylicacid reactant. Upon carrying out a thermal reaction without the use ofhalogen or a catalyst, then usually only about 50 to 75 wt. % of thepolyisobutylene will react. Chlorination helps increase the reactivity.For convenience, the aforesaid functionality ratios of mono- ordicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.8, etc.are based upon the total amount of polyolefin, that is, the total ofboth the reacted and unreacted polyolefin, used to make the product.

The reaction is preferably conducted in the substantial absence of O₂and water (to avoid competing side reactions), and to this end can beconducted in an atmosphere of dry N₂ gas or other gas inert under thereaction conditions. The reactants can be charged separately or togetheras a mixture to the reaction zone, and the reaction can be carried outcontinuously, semi-continuously or batchwise. Although not generallynecessary, the reaction can be carried out in the presence of a liquiddiluent or solvent, e.g., a hydrocarbon diluent such as minerallubricating oil, toluene, xylene, dichlorobenzene and the like. Thepolymer substituted mono- or dicarboxylic acid material thus formed canbe recovered from the liquid reaction mixture, e.g., after stripping thereaction mixture, if desired, with an inert gas such as N₂ to removeunreacted unsaturated carboxylic reactant.

If desired, a catalyst or promoter for reaction of the olefin polymerand monounsaturated carboxylic reactant (whether the olefin polymer andmonounsaturated carboxylic reactant are contacted in the presence orabsence of halogen (e.g., chlorine)) can be employed in the reactionzone. Such catalyst of promoters include alkoxides of Ti, Zr, V and Al,and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalystsor promoters will be generally employed in an amount of from about 1 to5,000 ppm by weight, based on the mass of the reaction medium.

PREPARATION OF THE DISPERSANT

The amido-amine is readily reacted with the selected polymer substitutedmono- or dicarboxylic acid material, e.g. alkenyl succinic anhydride, byheating an oil solution containing 5 to 95 wt. % of the polymersubstituted dicarboxylic acid material to about 100° to 250° C.,preferably 125° to 175° C., generally for 1 to 10, e.g. 2 to 6 hoursuntil the desired amount of water is removed. The heating is preferablycarried out to favor formation of imides and/or amides, rather thansalts. Generally from 1 to 5, preferably from about 1.5 to 3 moles ofmono- or dicarboxylic acid moiety content (e.g., grafted maleicanhydride or acrylic acid content) is used per equivalent of amido-aminereactant, e.g., amine.

An example of the reaction of an amido-amine reactant with a polymerdicarboxylic acid producing reactant is the reaction of polyisobutylenesuccinic anhydride (PIBSA) with a poly amido-amine having two terminal--NH₂ groups, which can be illustrated as follows: ##STR20## wherein xis an integer of from 0 to 10 and y is an integer of from 1 to 10, withthe proviso that the sum of x+y is at least 1, e.g., 1 to 20.

An example of the reaction of an amido-amine reactant with apolymer-substituted monocarboxylic acid producing reactant is thereaction of polyisobutylene propionic acid (PIBA) with a polyamido-amine having two terminal --NH₂ groups, which can be illustratedas follows: ##STR21## wherein x and y are each integers of from 0 to 10,with the proviso that the sum of x+y is at least 1, e.g., 1 to 20 andwherein Z¹ and Z² are the same or different and are each moieties of theformula: ##STR22##

It will be understood that the amido-amine reactant A can be employedalone or in admixture with any of the above described amines, such asthe polyalkylene polyamines, useful in preparing the amido-aminereactant.

Preferably, the polymer substituted mono- or dicarboxylic acid producingmaterial and amido-amine will be contacted for a time and underconditions sufficient to react substantially all of the primarynitrogens in the amido-amine reactant The progress of this reaction canbe followed by infrared analysis.

The dispersant-forming reaction can be conducted in a polar or non-polarsolvent (e.g., xylene, toluene, benzene and the like), and is preferablyconducted in the presence of a mineral or synthetic lubricating oil.

The nitrogen-containing dispersant materials of the instant invention asdescribed above can be post-treated by contacting saidnitrogen-containing dispersant materials with one or more post-treatingreagents selected from the group consisting of carbon disulfide, sulfur,sulfur chlorides, alkenyl cyanides, aldehydes, ketones, urea, thio-urea,guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbylphosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites,phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbylthiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyantes,epoxides, episulfides, formaldehyde or formaldehyde-producing compoundsplus phenols, and sulfur plus phenols, and C₁ to C₃₀ hydrocarbylsubstituted succinic acids and anhydrides (e.g., succinic anhydride,dodecyl succinic anhydride and the like), fumaric acid, itaconic acid,maleic acid, maleic anhydride, chloromaleic acid, chloromaleicanhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,and lower alkyl (e.g., C₁ to C₄ alkyl) acid esters of the foregoing,e.g., methyl maleate, ethyl fumarate, methyl fumarate, and the like.

Since post-treating processes involving the use of these post-treatingreagents is known insofar as application to high molecular weightnitrogen containing dispersants of the prior art, further descriptionsof these processes herein is unnecessary. In order to apply the priorart processes to the compositions of this invention, all that isnecessary is that reaction conditions, ratio of reactants, and the likeas described in the prior art, be applied to the novel compositions ofthis invention. The following U.S. patents are expressly incorporatedherein by reference for their disclosure of post-treating processes andpost-treating reagents applicable to the compositions of this invention:U.S. Pat. Nos. 3,087,936; 3,200,107; 3,254,025; 3,256,185; 3,278,550;3,281,428; 3,282,955; 3,284,410; 3,338,832, 3,344,069; 3,366,569;3,373,111; 3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093;3,533,945; 3,541,012; 3,639,242; 3,708,522; 3,859,318; 3,865,813;3,470,098; 3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909;3,245,910; 3,573,205; 3,692,681; 3,749,695; 3,865,740; 3,954,639;3,458,530; 3,390,086; 3,367,943; 3,185,704, 3,551,466; 3,415,750;3,312,619; 3,280,034; 3,718,663; 3,652,616; UK Pat. No. 1,085,903; UKPat. No. 1,162,436; U.S. Pat. No. 3,558,743.

The nitrogen containing dispersant materials of this invention can alsobe treated with polymerizable lactones (such as epsilon-caprolactone) toform dispersant adducts having the moiety --[C(O)(CH₂)_(z) O]_(m) H,wherein z is a number of from 4 to 8 (e.g., 5 to 7) and m has an averagevalue of from about 0 to 100 (e.g., 0.2 to 20). The dispersants of thisinvention can be post-treated with a C₅ to C₉ lactone, e.g.,epsilon-caprolactone, by heating a mixture of the dispersant materialand lactone in a reaction vessel in the absence of a solvent at atemperature of about 50° C. to about 200° C., more preferably from about75° C. to about 180° C., and most preferably from about 90° C. to about160° C., for a sufficient period of time to effect reaction. Optionally,a solvent for the lactone, dispersant material and/or the resultingadduct may be employed to control viscosity and/or the reaction rates.

In one preferred embodiment, the C₅ to C₉ lactone, e.g.,epsilon-caprolactone, is reacted with a dispersant material in a 1:1mole ratio of lactone to dispersant material. In practice, the ration oflactone to dispersant material may vary considerably as a means ofcontrolling the length of the sequence of the lactone units in theadduct. For example, the mole ratio of the lactone to the dispersantmaterial may vary from about 10:1 to about 0.1:1, more preferably fromabout 5:1 to about 0.2:1, and most preferably from about 2:1 to about0.4:1. It is preferable to maintain the average degree of polymerizationof the lactone monomer below about 100, with a degree of polymerizationon the order of from about 0.2 to about 50 being preferred, and fromabout 0.2 to about 20 being more preferred. For optimum dispersantperformance, sequences of from about 1 to about 5 lactone units in a roware preferred.

Catalysts useful in the promotion of the lactone-dispersant materialreactions are selected from the group consisting of stannous octanoate,stannous hexanoate, tetrabutyl titanate, a variety of organic based acidcatalysts and amine catalysts, as described on page 266, and forward, ina book chapter authored by R. D. Lundberg and E. F. Cox, entitled"Kinetics and Mechanisms of Polymerization: Ring OpeningPolymerization", edited by Frisch and Reegen, published by Marcel Dekkerin 1969, wherein stannous octanoate is an especially preferred catalyst.The catalyst is added to the reaction mixture at a concentration levelof about 50 to about 10,000 parts per weight of catalyst per one millionparts of the total reaction mixture.

The reactions of such lactones with dispersant materials containingnitrogen or ester groups is more completely described in copendingapplications Ser. Nos. 916,108; 916,217; 916,218; 916,287; 916,303;916,113; and 916,114, all filed on Oct. 7, 1986; and co-pending Ser. No.178,099 filed on Apr. 6, 1988; the disclosure of each of which is herebyincorporated by reference in its entirety.

The nitrogen-containing dispersant materials of this invention can alsobe post-treated by reaction with an alkyl acetoacetate or alkylthioacetate of the formula: ##STR23## wherein X^(a) is O or S, Rb is Hor Ra, and Ra is in each instance in which it appears independentlyselected from the group consisting of substituted and unsubstitutedalkyl or aryl (preferably alkyl of 1 to 6 carbon atoms, e.g., methyl,ethyl, etc.) to form an amino compound N-substituted by at least onetautomeric substituent of the formula: wherein R⁹ is as defined above.

The reaction is preferably effected at a temperature sufficiently highso as to substantially minimize the production of the enaminone andproduce, instead, the keto-enol tautomer. Temperatures of at least about150° C. are preferred to meet this goal although proper choice oftemperature depends on many factors, including reactants, concentration,reaction solvent choice, etc. Temperatures of from about 120° C. to 220°C., preferably from about 150° C. to 180° C. will generally be used. Thereaction of the nitrogen-containing dispersant material and the alkylacetonate and the alkyl thioacetate will liberate the correspondingHOR^(b) and HSR^(b) by-products, respectively. Preferably, suchby-products are substantially removed, as by distillation or strippingwith an inert gas (such as N₂), prior to use of the thus prepareddispersant adduct. Such distillation and stripping steps areconveniently performed at elevated temperature, e.g., at the selectedreaction temperature (for example, at 150° C. or higher). A neutraldiluent such as mineral oil may be used for the reaction.

The amount of alkyl aceto-acetate and/or alkyl thioacetate reactantsused can vary widely, and is preferably selected so as to avoidsubstantial excesses of these reactants. Generally, these reactants areused in a reactant:amine nitrogen-equivalent molar ratio of from about0.1 to 1:1, and preferably from about 0.5 to 1:1, wherein the moles ofamine nitrogen-equivalent is the moles of secondary nitrogens plus twicethe moles of primary nitrogens in the nitrogen-containing dispersantmaterial (e.g., polyisobutenyl succinimide) which is thus contacted withthe alkylacetonate or alkyl thioacetate. The reaction should also beconducted in the substantial absence of strong acids (e.g., mineralacids, such as HCl, HB₂, H₂ SO₄, H₃ PO₃ and the like, and sulfonicacids, such as para-toluene sulfonic acids) to avoid the undesiredside-reactions and decrease in yield to the adducts of this invention.

The reactions of such alkyl acetoacetates and thioacetoacetates withnitrogen-containing dispersant materials is more completely described incopending application Ser. No. 51,276, filed May 18, 1987, thedisclosure of which is hereby incorporated by reference in its entirety.

Further aspects of the present invention reside in the formation ofmetal complexes of the novel dispersant additives prepared in accordancewith this invention. Suitable metal complexes may be formed inaccordance with known techniques of employing a reactive metal ionspecies during or after the formation of the present dispersantmaterials Complex forming metal reactants include the metal nitrates,thiocyanates, halides, carboxylates, phosphates, thio-phosphates,sulfates, and borates of transition metals such as iron, cobalt, nickel,copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium,platinum, cadmium, lead, silver, mercury, antimony and the like. Priorart disclosures of these complexing reactions may be also found in U.S.Pat. Nos. 3,306,908 and Re. 26,433, the disclosures of which are herebyincorporated by reference in their entirety.

The processes of these incorporated patents, as applied to thecompositions of this invention, and the post-treated compositions thusproduced constitute a further aspect of this invention.

The dispersant-forming reaction can be conducted in a polar or non-polarsolvent (e.g., xylene, toluene, benzene and the like), and is preferablyconducted in the presence of a mineral or synthetic lubricating oil.

The nitrogen containing dispersants can be further treated by borationas generally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025(incorporated herein by reference thereto) This is readily accomplishedby treating the selected acyl nitrogen dispersant with a boron compoundselected from the class consisting of boron oxide, boron halides, boronacids and esters of boron acids in an amount to provide from about 0.1atomic proportion of boron for each mole of said acylated nitrogencomposition to about 20 atomic proportions of boron for each atomicproportion of nitrogen of said acylated nitrogen composition. Usefullythe dispersants of the inventive combination contain from about 0.05 to2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight ofsaid borated acyl nitrogen compound. The boron, which appears to be inthe product as dehydrated boric acid polymers (primarily (HBO₂)₃), isbelieved to attach to the dispersant imides and diimides as amine salts,e.g., the metaborate salt of said diimide.

Treating is readily carried out by adding from about 0.05 to 4, e.g. 1to 3 wt. % (based on the weight of said acyl nitrogen compound) of saidboron compound, preferably boric acid which is most usually added as aslurry to said acyl nitrogen compound and heating with stirring at fromabout 135° C. to 190, e.g. 140°-170° C., for from 1 to 5 hours followedby nitrogen stripping at said temperature ranges. Or, the borontreatment can be carried out by adding boric acid to the hot reactionmixture of the monocarboxylic acid material and amine while removingwater.

The ashless dispersants of this invention can be used alone or inadmixture with other dispersants such as esters derived from theaforesaid long chain hydrocarbon substituted dicarboxylic acid materialand from hydroxy compounds such as monohydric and polyhydric alcohols oraromatic compounds such as phenols and naphthols, etc. The polyhydricalcohols are the most preferred hydroxy compound and preferably containfrom 2 to about 10 hydroxy radicals, for example, ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, and other alkylene glycols in which the alkylene radicalcontains from 2 to about 8 carbon atoms. Other useful polyhydricalcohols include glycerol, mono-oleate of glycerol, monostearate ofglycerol, monomethyl ether of glycerol, pentaerythritol,dipentaerythritol, and mixtures thereof.

The ester dispersant may also be derived from unsaturated alcohols suchas allyl alcohol, cinnamyl alcohol, propargyl alcohol,1-cyclohexane-3-ol, and oleyl alcohol. Still other classes of thealcohols capable of yielding the esters of this invention comprise theether-alcohols and amino-alcohols including, for example, theoxy-alkylene, oxy-arylene-, amino-alkylene-, andamino-arylene-substituted alcohols having one or more oxy-alkylene,amino-alkylene or amino-arylene oxy-arylene radicals. They areexemplified by Cellosolve, Carbitol, N,N,N',N'-tetrahydroxy-trimethylenedi-amine, and ether-alcohols having up to about 150 oxy-alkyleneradicals in which the alkylene radical contains from 1 to about 8 carbonatoms.

The ester dispersant may be di-esters of succinic acids or acidicesters, i.e., partially esterified succinic acids; as well as partiallyesterified polyhydric alcohols or phenols, i.e., esters having freealcohols or phenolic hydroxyl radicals Mixtures of the above illustratedesters likewise are contemplated within the scope of this invention.

The ester dispersant may be prepared by one of several known methods asillustrated for example in U.S. Pat. No. 3,381,022. The esterdispersants may also be borated, similar to the nitrogen containingdispersants, as described above.

Hydroxyamines which can be reacted with the aforesaid long chainhydrocarbon substituted dicarboxylic acid materials to form dispersantsinclude 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol,N-(beta-hydroxy-propyl)-N'-(beta-aminoethyl-piperazine,tris(hydroxymethyl) amino-methane (also known astrismethylolaminomethane), 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)ethylamine, and the like. Mixtures of these orsimilar amines can also be employed. The above description ofnucleophilic reactants suitable for reaction with the hydrocarbylsubstituted dicarboxylic acid or anhydride includes amines, alcohols,and compounds of mixed amine and hydroxy containing reactive functionalgroups, i.e., amino-alcohols.

The tris(hydroxymethyl) amino methane (THAM) can be reacted with theaforesaid acid material to form amides, imides or ester type additivesas taught by U.K. 984,409, or to form oxazoline compounds and boratedoxazoline compounds as described, for example, in U.S. Pat. Nos.4,102,798; 4,116,876 and 4,113,639.

Other dispersants which can be employed in admixture with the novelamido-amine dispersants of this invention are those derived from theaforesaid long chain hydrocarbyl substituted dicarboxylic acid materialand the aforesaid amines, such as polyalkylene polyamines, e.g., longchain hydrocarbyl substituted succinimides Exemplary of such otherdispersants are those described in co-pending Ser. No. 95,056, filedSept. 9, 1987.

A preferred group of ashless dispersants are those derived frompolyisobutylene substituted with succinic anhydride groups and reactedwith amido-amine adducts formed by reacting polyethylene amines, e.g.,tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene andpolyoxypropylene amines, e.g., polyoxypropylene diamine,trismethylolaminomethane and pentaerythritol, and combinations thereof,with an acrylate-type compound of formula (XIV) above. One particularlypreferred dispersant combination involves a polyisobutene substitutedwith succinic anhydride groups and reacted with an amido-amine adductwhich has been formed by the reaction of (1) a polyalkylene polyamineand (2) an acrylate-type reactant selected from the group consisting oflower alkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl,iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid,acrylic acid, and the like).

The dispersants of the present invention can be incorporated into a fuelin any convenient way. Thus, these mixtures can be added directly to thefuel by dispersing or dissolving the same in the fuel at the desiredlevel of concentration of the dispersant. Such blending into theadditional fuel can occur at room temperature or elevated temperatures.Alternatively, the dispersants can be blended with a suitableoil-soluble solvent/diluent (such as benzene, xylene, toluene,lubricating base oils and petroleum distillates, including the variousnormally liquid fuels described in detail below) to form a concentrate,and then blending the concentrate with a fuel to obtain the finalformulation. Such dispersant concentrates will typically contain (on anactive ingredient (A.I.) basis) from about 3 to about 45 wt. %, andpreferably from about 10 to about 35 wt. %, dispersant additive, andtypically from about 30 to 90 wt. %, preferably from about 40 to 60 wt.%, base oil, based on the concentrate weight.

FUEL COMPOSITIONS

When the dispersants of this invention are used in normally liquidpetroleum fuels such as middle distillates boiling from about 65° to430° C., including motor gasolines, kerosene, diesel fuels, home heatingfuel oil, jet fuels, etc., a concentration of the additive in the fuelin the range of typically from about 0.001 to about 0.5, and preferably0.005 to about 0.1 weight percent, based on the total weight of thecomposition, will usually be employed. The properties of such fuels arewell known as illustrated, for example, by ASTM Specifications D #396-73(Fuel Oils) and D #439-73 (Gasolines) available from the AmericanSociety for Testing Materials ("ASTM"), 1916 Race Street, Philadelphia,Pa. 19103.

The distillate fuel oils will generally boil within the range of about120° C. to about 500° C., e.g. 150° to about 400° C. The fuel oil cancomprise atmospheric distillate or vacuum distillate, or cracked gas oilor a blend in any proportion of straight run and thermally and/orcatalytically cracked distillates, etc. The most common petroleumdistillate fuels are kerosene, jet fuels, diesel fuels and heating oils.The heating oil may be a straight atmospheric distillate, or it mayfrequently contain minor amounts, e.g. 0 to 35 wt. %, of vacuum gas oiland/or of cracked gas oils.

Oil soluble, as used herein, means that the additives are soluble in thefuel at ambient temperatures, e.g., at least to the extent of about 0.1wt. % additive in the fuel oil at 25° C.

The fuel compositions of this invention can contain, in addition to theproducts of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes, depositpreventers or modifiers such as triaryl phosphates, dyes, cetaneimprovers, anitoxidants such as 2,6-ditertiary-butyl-4-methylphenol,rust inhibitors, bacteriostatic agents, gum inhibitors, metaldeactivators, upper cylinder lubricants and the like.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (A.I.) content of theadditive, and/or upon the total weight of any additive-package, orformulation which will be the sum of the A.I. weight of each additiveplus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight, unless otherwise notedand which include preferred embodiments of the invention. In theExamples, SA:PIB ratios are based upon the total PIB charged to thereactor as starting material, i.e., both the PIB which reacts and thePIB which remains unreacted.

PREPARATION OF POLYISOBUTYLENE SUCCINIC ANHYDRIDE (PIBSA) EXAMPLE 1

A polyisobutenyl succinic anhydride having a succinic anhydride (SA) topolyisobutenylene mole ratio (i.e., a SA:PIB ratio) of 1.04 is preparedby heating a mixture of 100 parts of polyisobutylene (940 M_(n) /M_(n)=2.5) with 13 parts of maleic anhydride to a temperature of about 220°C. When the temperature reaches 120° C., the chlorine addition is begunand 10.5 parts of chlorine at a constant rate are added to the hotmixture for about 5.5 hours. The reaction mixture is then heat soaked at220° C. for about 1.5 hours and then stripped with nitrogen for aboutone hour. The resulting polyisobutenyl succinic anhydride has an ASTMSaponification Number of 112. The PIBSA product is 90 wt. activeingredient (A.I.), the remainder being primarily unreacted PIB.

EXAMPLE 2

A polyisobutenyl succinic anhydride (PIBSA) having a SA:PIB ratio of1.24, is prepared by heating a mixture of 100 parts of polyisobutylene(1320 M_(n) ; M_(n) /M_(n) =2.5) with 11 parts of maleic anhydride to atemperature of about 220° C. When the temperature reaches 120° C., thechlorine addition is begun and 10 parts of chlorine at a constant rateare added to the hot mixture for about 5 hours. The reaction mixture isthen heat soaked at 220° C. for about 1.5 hours and then stripped withnitrogen for about one hour. The resulting polyisobutenyl succinicanhydride was diluted with S150 mineral oil to obtain a product havingan ASTM Saponification Number of 69. The PIBSA product is 59 wt. %active ingredient (A.I.), the remainder being primarily unreacted PIBand mineral oil.

EXAMPLE 3

A polyisobutenyl succinic anhydride having a SA:PIB ratio of 1.13 isprepared by heating a mixture of 100 parts of polyisobutylene (2225M_(n) ; M_(n) /M_(n=) 2.5) with 6.11 parts of maleic anhydride to atemperature of about 220° C. When the temperature reaches 120° C., thechlorine addition is begun and 5.07 parts of chlorine at a constant rateare added to the hot mixture for about 5.5 hours. The reaction mixtureis then heat soaked at 220° C. for about 1.5 hours and then strippedwith nitrogen for about one hour. The resulting polyisobutenyl succinicanhydride has an ASTM Saponification Number of 54. The PIBSA product is80 wt. % active ingredient (A.I.), the remainder being primarilyunreacted PIB.

Preparation of Dispersants

A series of dispersants were prepared by reacting the selected PIBSA,prepared as in Examples 1-3 above, with one of two amido-amines or witha polyalkylene polyamine, tetraethylene pentamine (TEPA). Amido-amine Iis prepared by reacting TEPA with methyl acrylate at a 2:1 TEPA:methylacrylate molar ratio, to form a product mixture having 30.1 wt. % totalN, 8.2 wt. % primary N, and containing about 50 wt. % unreacted TEPA.Amido-amine II is prepared similarly, except that a 1.5:1 TEPA:methylacrylate molar ratio is employed, to form a product mixture containing28.3 wt. % total N, 6.1 wt. % primary N, and about 25 wt. % unreactedTEPA.

The amination reactions were carried out as follows:

EXAMPLE 4

A mixture of 200 parts by weight of the PIBSA product formed in Example1 and 188 parts of S150 mineral oil was heated to 150° C. under N₂. Then32.3 parts of amido-amine I were added dropwise while stirring and lightnitrogen sparging. The mixture was nitrogen stripped at 150° C. for 3hours and then filtered. The oil solution was found to have the nitrogencontent of 2.37 wt % and a kinematic viscosity of 107.4 cSt at 100° C.

EXAMPLE 5

A mixture of 200 parts by weight of the PIBSA product formed in Example1 and 200 parts of S150 mineral oil was heated to 150° C. under N₂. Then43.4 parts of amido-amine II were added dropwise while stirring andlight nitrogen sparging. The mixture was nitrogen stripped at 150° C.for 3 hours and then filtered. The oil solution was found to have thenitrogen content of 2.86 wt % and a kinematic viscosity of 135.7 cSt at100° C.

EXAMPLE 6

A mixture of 200 parts by weight of the PIBSA product formed in Example2 and 55 parts of S150 mineral oil was heated to 150° C. under N₂. Then21 parts of amido-amine I were added dropwise while stirring and lightnitrogen sparging. The mixture was nitrogen stripped at 150° C. for 3hours and then filtered. The oil solution was found to have the nitrogencontent of 2.39 wt % and a kinematic viscosity of 220.8 cSt at 100° C.

EXAMPLE 7

A mixture of 200 parts by weight of the PIBSA product formed in Example2 and 62 parts of S150 mineral oil was heated to 150° C. under N₂. Then28.2 parts of amido-amine II were added dropwise while stirring andlight nitrogen sparging. The mixture was nitrogen stripped at 150° C.for 3 hours and then filtered The oil solution was found to have thenitrogen content of 2.86 wt % and a kinematic viscosity of 207.4 cSt at100.C.

A mixture of 200 parts by weight of the PIBSA product formed in Example3 and 126 parts of S150 mineral oil was heated to 150° C. under N₂. Then15.9 parts of amido-amine I were added dropwise while stirring and lightnitrogen sparging. The mixture was nitrogen stripped at 150° C. for 3hours and then filtered. The oil solution was found to have the nitrogencontent of 1.51 wt % and a kinematic viscosity of 494.1 cSt at 100° C.

EXAMPLE 9

A mixture of 200 parts by weight of the PIBSA product formed in Example3 and 132 parts of S150 mineral oil was heated to 150° C. under N₂. Then21.3 parts of amido-amine II were added dropwise while stirring andlight nitrogen sparging. The mixture was nitrogen stripped at 150° C.for 3 hours and then filtered. The oil solution was found to have thenitrogen content of 1.83 wt % and a kinematic viscosity of 484.2 cSt at100° C.

COMPARATIVE EXAMPLE A

A mixture of 200 parts by weight of the PIBSA product formed in Example1 and 174.5 parts of S150 mineral oil was heated to 150° C. under N₂.Then 17.9 parts of tetraethylenepentaamine were added dropwise whilestirring and light nitrogen sparging. The mixture was nitrogen strippedat 150° C. for 3 hours and then filtered. The oil solution was found tohave the nitrogen content of 1.72 wt % and a kinematic viscosity of156.3 cSt at 100° C.

COMPARATIVE EXAMPLE B

A mixture of 200 parts by weight of the PIBSA product formed in Example2 and 42 parts of S150 mineral oil was heated to 150° C. under N₂. Then11.6 parts of tetraethylenepentaamine were added dropwise while stirringand light nitrogen sparging. The mixture was nitrogen stripped at 150°C. for 3 hours and then filtered. The oil solution was found to have thenitrogen content of 1.65 wt % and a kinematic viscosity of 213.0 cSt at100° C.

COMPARATIVE EXAMPLE C

A mixture of 200 parts by weight of the PIBSA product formed in Example3 and 119 parts of S150 mineral oil was heated to 150° C. under N₂. Then8.8 parts of tetraethylenepentaamine were added dropwise while stirringand light nitrogen sparging. The mixture was nitrogen stripped at 150°C. for 3 hours and then filtered. The oil solution was found to have thenitrogen content of 1.05 wt % and a kinematic viscosity of 487.8 cSt at100° C.

The product dispersants thereby obtained are summarized as set forth inTable I below.

                  TABLE I                                                         ______________________________________                                        Example PIB                        VIS 100° C.                         No.     Mn       Amine        % N  cSt                                        ______________________________________                                        4        940     Amido-amine I                                                                              2.37 107.4                                      5        940     Amido-amine II                                                                             2.86 135.2                                      Compar. A                                                                              940     TEPA         1.72 156.3                                      6       1300     Amido-amine I                                                                              2.39 220.8                                      7       1300     Amido-amine II                                                                             2.86 207.4                                      Compar. B                                                                             1300     TEPA         1.65 213.0                                      8       2250     Amido-amine I                                                                              1.51 494.1                                      9       2250     Amido-amine II                                                                             1.83 484.2                                      Compar. C                                                                             2250     TEPA         1.05 487.8                                      ______________________________________                                    

EXAMPLE 10

A mixture of 1551 parts by weight of the PIBSA product formed in Example3 and 1181 parts of S150 mineral oil was heated to 150° C. under N₂.Then 150 parts of amido-amine II were added dropwise while stirring andlight nitrogen sparging. The mixture was nitrogen stripped at 150° C.for 3 hours and then filtered. The oil solution was found to have thenitrogen content of 1.51 wt % and a kinematic viscosity of 473.4 cSt at100° C.

COMPARATIVE EXAMPLE D

A mixture of 1800 parts by weight of the PIBSA product formed in Example3 and 1163 parts of S150 mineral oil was heated to 150° C. under N₂.Then 94 parts of tetraethylenepentaamine were added dropwise whilestirring and light nitrogen sparging for 1 hour. The mixture wasnitrogen stripped at 150° C. for 1.5 hours. 39.5 parts of boric acid areadded over 1.5 hours while stirring at 163° C. followed by N₂ strippingfor 2 hours, cooling and filtering. The oil solution was found to havethe nitrogen content of 0.97 wt %, a boron content of 0.28 wt % and akinematic viscosity of 896 cSt at 100° C.

EXAMPLE 11 Preparation of Amido Amine.

To a stirred reaction vessel was added 1.5 moles oftetraethylenepentamine (TEPA) at room temperature, followed by 1 mole ofethyl acrylate, under a N₂ blanket. The resulting exothermic reactionraised the reaction mass, temperature to about 75° C. Then an infra-redanalysis (IR) was made of the reaction mass, which showed thedisappearance of the double bond of the ethyl acrylate, but revealedester groups to be still present. A gas chromatographic analysis of thereaction mass was also then taken, which showed unreacted TEPA stillpresent.

An esterification catalyst, stannous octanoate, was then added (1 drop)to the reaction mass, and the temperature of the reaction vessel wasincreased to 130° to 135° C. with mild N₂ sweeping. The by-productalcohol (ethanol) was removed as a vapor from the reaction vessel withthe sweep N₂, and the progress of the reaction was followed by IR untilthe ester absorption band disappeared. The reaction mass was stirred foradditional 1 hour at 130° to 135° C. to ensure completion of thereaction. A total reaction time of 6 hours was used. The resultingproduct mixture containing the amido-amine was analyzed and was found tocontain 4.8 milliequivalents of primary amine per gram of amido-amineand a nitrogen content of 30.1 wt %.

EXAMPLE 12

The procedure of Example 11 was repeated except that the esterificationcatalyst comprised titanium tetrabutoxide, and similar results wereobtained.

EXAMPLE 13

A series of gasolines are prepared having a Reid vapor pressure of 8.4psi and containing the indicated amounts of the dispersant productmixtures prepared as described above:

                  TABLE A                                                         ______________________________________                                        Gasoline        Dispersant                                                    Composition     Ex. No.: (wt %)                                               ______________________________________                                        A               4        0.002                                                B               5        0.02                                                 C               6        0.008                                                D               7        0.1                                                  E               8        0.3                                                  F               9        0.015                                                G               4        0.001                                                H               11       0.09                                                 I               12       0.005                                                J               11       0.05                                                 ______________________________________                                    

EXAMPLE 14

A series of diesel fuels are prepared containing the indicated amountsof the dispersant product mixtures prepared as described above:

                  TABLE B                                                         ______________________________________                                        Diesel Fuel     Dispersant                                                    Composition     Ex No.   (wt %)                                               ______________________________________                                        A               4        0.002                                                B               5        0.02                                                 C               6        0.008                                                D               7        0.1                                                  E               8        0.3                                                  F               9        0.015                                                G               4        0.001                                                H               11       0.09                                                 I               12       0.005                                                J               11       0.05                                                 ______________________________________                                    

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art withoutdeparting from the spirit of the invention.

What is claimed is:
 1. A process for producing a dispersant useful as anoil additive which comprises:(a) providing a long chain hydrocarbylsubstituted mono- or dicarboxylic acid producing material formed byreacting an olefin polymer of C₂ to C₁₀ monoolefin having a numberaverage molecular weight of about 300 to 10,000 and at least one of a C₄to C₁₀ monounsaturated dicarboxylic acid material and a C₃ to C₁₀monounsaturated monocarboxylic acid material, said acid producingmaterial having an average of at least about 0.3 dicarboxylic acidproducing moieties, per molecule of said olefin polymer present in thereaction mixture used to form said acid producing material; (b)providing an amido-amine compound having at least one primary aminogroup prepared by reacting at least one polyamine with at least onealpha, beta-unsaturated compound of the formula: ##STR24## wherein X issulfur or oxygen, Y is --OR⁴,--SR⁴, or --NR⁴ (R⁵) , and R¹, R², R³, R⁴and R⁵ are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl; and (c) contacting the said acid producingmaterial with said amido-amine compound under conditions sufficient toeffect reaction of at least a portion of the primary amino groups onsaid amido-amine compound with at least a portion of the acid-producinggroups in said acid producing material, to form said dispersant.
 2. Theprocess according to claim 1 wherein said polyamine comprises aminescontaining from 2 to 60 carbon atoms and from 2 to 12 nitrogen atoms permolecule.
 3. The process according to claim 2, wherein said polyaminecomprises a polyalkylenepolyamine wherein each said alkylene groupcontains from 2 to 40 carbons and said polyalkylenepolyamine containsfrom 5 to about 9 nitrogen atoms per molecule.
 4. The process accordingto claim 1, wherein said hydrocarbyl substituted acid producing materialcomprises a hydrocarbyl substituted C₄ to C₁₀ monounsaturateddicarboxylic acid producing material which comprises polyisobutylene ofabout 900 to 5000 number average molecular weight substituted withsuccinic anhydride moieties, said amine comprises polyalkylenepolyaminewherein each said alkylene group contains from 2 to 6 carbons and saidpolyalkyenepolyamine contains from 5 to 9 nitrogen atoms per molecule,and an acrylate-type compound comprising at least one member selectedfrom the group consisting of methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, methyl methacrylate, ethyl methacylate, propylmethacrylate, and butyl methacrylate.
 5. The process according to claims1 or 4, wherein said polyamine comprises polyethylenepolyamine.
 6. Theprocess according to claims 1 or 4, wherein said dispersant is boratedto provide from about 0.05 to 2.0 weight percent boron in said borateddispersant.
 7. The process according to claim 1, wherein the ratio ofacid producing moieties per molecule of olefin polymer in saiddispersant is from about 0.9 to 1.3
 8. The process of claim 7, whereinsaid number average molecular weight of said fist olefin polymer is fromabout 1300 to 4,000.
 9. The process of claim 8, wherein saidmonounsaturated acid material comprises maleic anhydride.